Amino derivative of hydroxy diphenyls



Patented June 11, 1935 2,004,914

UNITED STATES PATENT. OFFICE AMINO DERIVATIVE.OF HYDROXY DIPHENYLS William D. Woke Akron, Ohio, assignor to Wingfoot Corporation, Wilmington, Del., a corporation of Delaware No Drawing. A plication December 18, 1930,. Serial No. 503,233

I (Cl. 260-128) 9 Claims. h This invention relates'to a new class of organic A corresponding reaction product of ortho hycompounds and it has particular relation to dedroxy diphenyl and hexamethylene tetramine rivatives of hydroxy diphenyl and amino matemay be obtained by adding a molar proportion of rials. hexamethylene tetramine, dissolved in water, to One object of the invention is to provide ma- 3. molar proportion of ortho hydroxy diphenyl 5 terials of the above indicated class which are dissolvedinalcohol. The material may be formed relatively easy to manufacture by means of simple by the addition of formaldehyde to a solution of reactions and which involve the use of relatively. hydroxy diphenyl in ammoniacal alcohol. The inexpensive ingredients. Other objects and 'adcompound readily crystallizes from alcohol in a 10 vantages will become apparent as the description comparatively high state of purity. The crystals of the invention proceeds. thus formed are clustered together as pure white Hydroxy diphenyl, a material having the forneedles having a melting point of 161- to 162 demula 1 grees C. These crystals are soluble in dilute sodium hydroxide but are insoluble in cold dilute l5 OO I hydrochloric acid. They are readily decomposed l5 in the acid solution merely by the application of is Obtained as a y-p fl 1n the maflufactuleof heat to the latter and in so decomposing formalphenol from chlor benzene (Industrial and Eng. dehyde ammonium chloride and ortho hydroxy Chem. volume 20, page 114) Heretofore, hydroxy diphenyl are vliberated 2o diphenyl has had little or no use in commercial A corresponding reaction product of p practice. droxy diphenyl and beta naphthylamine is pre- Th is invention involves} the discovery that t pared by dissolving equi-molar proportions of the relatively valueless matenal may readily be caused twohbasic constituents in three or fou parts f to react with amino bodies to form materials alcohol by t application of h t Upon cools ou t t av e general formula ing this solution, the reaction product is depos- 25 ited in the form of glistening white plates having @O a sharp melting point ranging from..130 to 131 degrees C. The yield of material thus obtained where R is a substituted or unsubstituted hydrois approximately 67.5 percent of the theoretically 3 carbon grouping, either aliphatic, aryl or heteropossible alue, 0

cyclic. Some of the materials of this class are Para. hydroxy] diphenyl likewise reacts with found to be valuable in the rubber industry as ethylene diamine in substantially the same manaccelerators of vulcanization or antioxidants or ner asortho hydroxy diphenyl. This reaction is age retarders in rubber compounds. preferably conducted in alcoholic solution at nor- As a specific example of a material formed by mal or room temperatures and under'atmospheric the interaction of hydroxy diphenyl and an amine, pressures. The reactionproduct is obtained in attention is called to the derivative of ortho the form of shining silvery white plates which hydroxy diphenyL and ethylene diamine which are moderately soluble in alcohol and which'melt has the formula at a 'temperature of 137 to 138 degrees C. Para 4o -CH2 NH2H0C6H4CH5 hydroxy diphenyl also reacts with cyclo 'hexyl amine merely by adding the amine to an alcohol HPNHHO solution of para hydroxy diphenyl. This reaction, This material is readily prepared in yields of like most of the reactions whichhave previously approximately 95 percent of theoretical value been described, occurs at normal room temperamerely by intermixing a molar' proportion of tures and at atmospheric pressures. The'reacethylene diamine with two of ortho hydroxy dition product crystallizes from the solution as aphenyl in alcoholic solution at approximately glistening white crystalline powder which meltsnormal room temperatures and atmospheric presat a temperature of 108 to 109 degrees C. The sures. Upon the addition of water to this soluyield thus obtained is approximately 68.5 percent tion, an amber colored oil settles out. This'oil, of the theoretical-value. The behaviour of para 50 upon being allowed to stand for a short period of hydroxy diphenyl toward hexamethylene tetratime, solidifies into a yellowish solid which may mine is strictly analogous to that of ortho hybe broken up with ease and which is found to condroxy. diphenyl and the amine compound -besist of amass of granular crystals having a meltcause, upon the addition of hexamethylene tetraing point of 78 to 80 c. mine in water solution toan alcoholic solution 55 of para hydroxy diphenyl at normal temperatures and pressures, a reaction product is obtainedtained by the addition of formaldehyde to an ammoniacal solution of para hydroxy diphenyl in alcohol. The melting point of the resultant material in either case is approximately 152 degrees C. As has already been intimated, the reaction products thus obtained "are in a relatively high state of purity. The reactions are also exceedingly simple in character and may be conducted without use of any special apparatus or any particular precautions in the regulation of the conditions under which the reactions occur. It is to be understood that the invention is not limited to the specific reaction products discussed, but also includes the reaction products of either para or ortho hydroxy diphenyl with numerous other amines or basic nitrogen containing bodies such as .ethylamine, butylamine, benzylamine and aniline. 'Hydroxy diphenyl may also be caused to react with the amino derivative of hydroxy diphenyl which is obtained by the reduction of the nitro derivative of hydroxy diphenyl.

Although I have described the preferred forms of the invention, it will be apparent to those skilled in the art that the invention is not limited thereto, but that various modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims. It is intended that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty reside in the invention.

What I claim is:

1. The addition product of a mono hydroxy diphenyl and an amine of the group consisting of primary aliphatic monoand diamines, primary aromatic mono amines of the benzene and naphthalene series, benzyl amine, cyclohexyl amine and hexamethylene tetra amine.

2. The addition product of a hydroxy diphenyl and a primary aliphatic diamine.

3. The addition product of a hydroxyl diphenyl and a primary aliphatic mono amine.

4. The addition product of a mono hydroxy diphenyl and a primary aliphatic mono amine.

5. The addition product of a mono hydroxy diphenyl and a primary aliphatic diamine.

6. The addition product of a mono hydroxy diphenyl and a primary aromatic mono amine of the benzene and naphthalene series.

'7. The addition product of hydroxy diphenyl and beta naphthylamine.

8. The addition product of hydroxy diphenyl and ethylene diamine.

9. The addition product of hydroxy diphenyl and cyclohexyl amine.

WILLIAM D. WOLFE. 

